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1.
William Clegg Ross W. Harrington Kazem Barati Mohammad Hossein Habibi Morteza Montazerozohori Arash Lalegani 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):578-583
Reaction of copper(I) thiocyanate and triphenylphosphane with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca2en, (1); systematic name (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]}, C20H18N4O4, in a 1:1:1 molar ratio in acetonitrile resulted in the formation of the complex {(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ2N,N′}(thiocyanato‐κN)(triphenylphosphane‐κP)copper(I)], [Cu(NCS)(C20H18N4O4)(C18H15P)] or [Cu(NCS)(Nca2en)(PPh3)], (2). The Schiff base and copper(I) complex have been characterized by elemental analyses, IR, electronic and 1H NMR spectroscopy, and X‐ray crystallography [from synchrotron data for (1)]. The molecule of (1) lies on a crystallographic inversion centre, with a trans conformation for the ethylenediamine unit, and displays significant twists from coplanarity of its nitro group, aromatic ring, conjugated chain and especially ethylenediamine segments. It acts as a bidentate ligand coordinating via the imine N atoms to the CuI atom in complex (2), in which the ethylenediamine unit necessarily adopts a somewhat flattened gauche conformation, resulting in a rather bowed shape overall for the ligand. The NCS− ligand is coordinated through its N atom. The geometry around the CuI atom is distorted tetrahedral, with a small N—Cu—N bite angle of 81.56 (12)° and an enlarged opposite angle of 117.29 (9)° for SCN—Cu—P. Comparisons are made with the analogous Schiff base having no nitro substituents and with metal complexes of both ligands. 相似文献
2.
Roza Dimeska Jan Wikaira Garry M. Mockler Ray J. Butcher 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(5):538-544
The structures of three copper‐containing complexes, namely (benzoato‐κ2O,O′)[(E)‐2‐({[2‐(diethylamino)ethyl]imino}methyl)phenolato‐κ3N,N′,O]copper(II) dihydrate, [Cu(C7H5O2)(C13H19N2O)]·2H2O, 1 , [(E)‐2‐({[2‐(diethylamino)ethyl]imino}methyl)phenolato‐κ3N,N′,O](2‐phenylacetato‐κ2O,O′)copper(II), [Cu(C8H7O2)(C13H19N2O)], 2 , and bis[μ‐(E)‐2‐({[3‐(diethylamino)propyl]imino}methyl)phenolato]‐κ4N,N′,O:O;κ4O:N,N′,O‐(μ‐2‐methylbenzoato‐κ2O:O′)copper(II) perchlorate, [Cu2(C8H7O2)(C12H17N2O)2]ClO4, 3 , have been reported and all have been tested for their activity in the oxidation of d ‐galactose. The results suggest that, unlike the enzyme galactose oxidase, due to the precipitation of Cu2O, this reaction is not catalytic as would have been expected. The structures of 1 and 2 are monomeric, while 3 consists of a dimeric cation and a perchlorate anion [which is disordered over two orientations, with occupancies of 0.64 (4) and 0.36 (4)]. In all three structures, the central Cu atom is five‐coordinated in a distorted square‐pyramidal arrangment (τ parameter of 0.0932 for 1 , 0.0888 for 2 , and 0.142 and 0.248 for the two Cu centers in 3 ). In each species, the environment about the Cu atom is such that the vacant sixth position is open, with very little steric crowding. 相似文献
3.
Hiroo Nakagawa Yoshiyuki Kani Masanobu Tsuchimoto Shigeru Ohba Hideaki Matsushima Tadashi Tokii 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(1):12-16
In the crystals of bis(pyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C5H5N)2], (I), the dinuclear CuII complexes have cage structures with Cu?Cu distances of 2.632 (1) and 2.635 (1) Å. In the crystals of bis(2‐methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C6H7N)2], (II), bis(3‐methylpyridine‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C6H7N)2], (III), and bis(quinoline‐N)tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II), [Cu2(C5H11O2Si)4(C9H7N)2], (IV), the centrosymmetric dinuclear CuII complexes have a cage structure with Cu?Cu distances of 2.664 (1), 2.638 (3) and 2.665 (1) Å, respectively. In the crystals of catena‐poly[tetrakis(μ‐trimethylsilylacetato‐O:O′)dicopper(II)], [Cu2(C5H11O2Si)4]n, (V), the dinuclear CuII units of a cage structure are linked by the cyclic Cu—O bonds at the apical positions to form a linear chain by use of a glide translation. 相似文献
4.
The copper-catalyzed oxidation of hydrazine by iron(III) in acid solution follows the rate law -d[Fe(III)]/dt = kKh[Cu(II)]2/(Kh + [H+]), where Kh is the hydrolysis constant of Cu2+, k was found to be 8.8±0.8, 13.2±1.4 and 17.5±1.3 min?1 at 35, 40, and 45°C respectively and μ= 0.2 mol/L. The composition of the activated complex is Cu2+, CuOH+, N2H4, H+ or others. Perhaps several hydrazine complexes of Cu(II) participate in the reaction and one of them isolated was Cu(N2H4)2(HSO4)2. Study on the oxidation of this complex is also in conformity with the above rate law. 相似文献
5.
Ahmet Coşkun Funda Yılmaz Emine G. Akgemci 《Journal of inclusion phenomena and macrocyclic chemistry》2008,60(3-4):393-400
4-(Chloroacetyl)diphenyl ether was synthesized from chloroacetyl chloride and diphenyl ether in the presence of AlCl3 as catalyst in a Friedel-Crafts reaction. Then, its keto oxime and dioxime derivatives were prepared. 4-phenoxy-(N-4-chlorophenylamino)phenylglyoxime (H2L) was synthesized from 4-(phenoxy)chlorophenylglyoxime and 4-chloroaniline. Ni(II), Co(II) and Cu(II) complexes of H2L were obtained. The mononuclear Ni(II), Co(II) and Cu(II) complexes of H2L have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The structure of the ligand was identified by FT-IR, 1H NMR, 13C NMR, 13C NMR (APT) spectroscopy and elemental analysis data. The structures of the complexes were characterized on the basis of FT-IR,
ICP-AES, UV-Vis, elemental analysis, magnetic susceptibility measurements, and cyclic voltammetry. The electrochemical measurements
were obtained by using cyclic voltammetry in DMF solution at room temperature. The electrochemical behaviors of H2L and its complexes showed that the redox process of H2L has one irreversible oxidation wave, whereas the redox processes of the complexes have both oxidation and reduction waves
with metal centered. 相似文献
6.
Katherine A. Bussey Annie R. Cavalier Jennifer R. Connell Margaret E. Mraz Kayode D. Oshin Tomislav Pintauer Allen G. Oliver 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):526-533
The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the CuI and CuII oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena‐poly[[copper(I)‐μ2‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ5N,N′,N′′:C2,C3] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two CuI complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the CuI atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with CuII show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu2Cl2 moiety. 相似文献
7.
Marius Lupu Adnana Zaulet Prof. Dr. Francesc Teixidor Prof. Dr. Eliseo Ruiz Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6888-6897
The metallacarborane [3,3′‐Co(1,2‐closo‐C2B9H11)2]? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C2B9H7I4)2]? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed. 相似文献
8.
Manisha Singla Pavan Mathur Manisha Gupta M. S. Hundal 《Transition Metal Chemistry》2008,33(2):175-182
New bis-benzimidazole based diamide ligands N, N′-bis(2-methyl benzimidazolyl)-benzene-1,3-dicarboxamide [GBBA] and N-Octyl-N, N′-bis(2-methyl benzimidazolyl)-benzene- 1,3-dicarboxamide [O-GBBA] have been synthesized and utilized to prepare Cu(II) complexes
of general composition [Cu(GBBA)X
2] · nH2O and [Cu(O-GBBA)X2] · n H2O, where X is an exogenous anionic ligand (X = Cl−, NO3−, SCN−). The oxidation of electron deficient olefins has been investigated using [Cu(O-GBBA)X2] · nH2O as catalyst and TBHP as an alternate source of oxygen. The respective ketonic products have been isolated and characterized
by 1H-NMR. The complex [Cu(GBBA)(NO3)2] · 4H2O has been characterized structurally. It crystallizes in a monoclinic space group C2/c. Low temperature EPR spectra have been obtained for the complexes that shows gII > gI > 2.0024, indicating a tetragonal geometry in the solution state. The complexes display a quasi reversible redox wave due
to the Cu(II)/Cu(I) reduction process. The E1/2 values shift anodically as NO3− < SCN− < Cl−. 相似文献
9.
Vladimir V. Bon 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(10):m300-m302
The title compound, [(Z)‐4‐allyl‐2‐(2‐hydroxybenzylidene)thiosemicarbazide‐κS][(E)‐4‐allyl‐1‐(2‐oxidobenzylidene)thiosemicarbazidato‐κ3O,N1,S]copper(II) monohydrate, [Cu(C11H11N3OS)(C11H13N3OS)]·H2O, crystallized as a rotational twin in the monoclinic crystal system (space group Cc) with two formula unit (Z′ = 2) in the asymmetric unit, one of which contains an allyl substituent disordered over two positions. The CuII atom exhibits a distorted square‐planar geometry involving two differently coordinated thiosemicarbazone ligands. One ligand is bonded to the CuII atom in a tridentate manner via the phenolate O, azomethine N and thioamide S atoms, while the other coordinates in a monodentate manner via the S atom only. The complex is stabilized by an intramolecular hydrogen bond, which creates a six‐membered pseudo‐chelate metalla‐ring. The structure analysis indicates the presence of the E isomer for the tridentate ligand and the Z isomer for the monodentate ligand. The crystal structure contains a three‐dimensional network built from intermolecular O—H...O, N—H...O, O—H...N and N—H...S hydrogen bonds. 相似文献
10.
Fredy R. Prez Julio Belmar Claudio Jimnez Yanko Moreno Patricio Hermosilla Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(6):m318-m320
The title compound, [Cu(C19H26N3O)2], is the first reported complex of the alkylpyrazolone‐derived ligand 1‐n‐hexyl‐3‐methyl‐4‐[1‐(phenylimino)propyl]‐1H‐pyrazol‐5(4H)‐one. The most notable feature is the imine–enol character presented by the ligand due to coordination, in spite of its enamine–ketone structure in the free state. The ligand chelates through N and O atoms, resulting in a square‐planar coordination around the CuII atom, which lies on an inversion centre. 相似文献
11.
Zakieh Yousefi Hossein Eshtiagh‐Hosseini Alireza Salimi Janet Soleimannejad 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(5):386-393
In the title compound, [Cu(C7H3N2O4)(C4H5N2)(H2O)], (I), pyridine‐2,6‐dicarboxylate (pydc2−), 2‐aminopyrimidine and aqua ligands coordinate the CuII centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc2− ligand. Because of the presence of Cu...Xbridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the CuII centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment. 相似文献
12.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(11):1024-1029
The crystal structures of mono‐ and dinuclear CuII trifluoromethanesulfonate (triflate) complexes with benzyldipicolylamine (BDPA) are described. From equimolar amounts of Cu(triflate)2 and BDPA, a water‐bound CuII mononuclear complex, aqua(benzyldipicolylamine‐κ3N ,N′ ,N ′′)bis(trifluoromethanesulfonato‐κO )copper(II) tetrahydrofuran monosolvate, [Cu(CF3SO3)2(C19H19N3)(H2O)]·C4H8O, (I), and a triflate‐bridged CuII dinuclear complex, bis(μ‐trifluoromethanesulfonato‐κ2O :O ′)bis[(benzyldipicolylamine‐κ3N ,N′ ,N ′′)(trifluoromethanesulfonato‐κO )copper(II)], [Cu2(CF3SO3)4(C19H19N3)2], were synthesized. The presence of residual moisture in the reaction medium afforded water‐bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single‐crystal X‐ray structure analysis reveals that the CuII centres adopt slightly distorted octahedral geometries in both complexes. The metal‐bound water molecule in (I) is involved in intermolecular O—H…O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak intermolecular C—H…F(triflate) and C—H…O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis. 相似文献
13.
Summary Reactions of bis(1-oxopyridine-2-thione) NiII or CuII with 2,2-bipyridine (bipy) or 1,10-phenanthroline (phen) yield complexes of stoichiometry: Ni(C5H4NOS)2L {L = bipy, two isomers: (1) and (2), L = phen, one isomer (3)} and Cu(C5H4NOS)2(phen)·0.75CHCl3
(4). The spectroscopy (i.r., u.v.-vis., e.s.r.) and magnetism studies of the above complexes are described. On the basis of conductivity, the CuII-phen complex has been formulated as [Cu(C5H4NOS)(phen)2][Cu(C5H4NOS)3]·1.5CHCl3
(4). The vis. absorption spectra support similar octahedral structures for the minor bipy isomer (2) and for the NiII-phen complex [(3)], whereas the major isomer [(1)] has a different structure. The e.s.r. spectrum of the CuII-phen complex (4) is commensurate with an elongated octahedral structure. New methods for the preparation and spectroscopy of M(C5H4NOS)2 (M = Mn, Ni, Cu or Zn) compounds have been investigated. 相似文献
14.
Dr. Maximilian N. Kopylovich Dr. Archana Mizar Dr. M. Fátima C. Guedes da Silva Dr. Tatiana C. O. Mac Leod Dr. Kamran T. Mahmudov Prof. Armando J. L. Pombeiro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):588-600
A one‐pot template condensation of 2‐(2‐(dicyanomethylene)hydrazinyl)benzenesulfonic acid (H2L1, 1 ) or 2‐(2‐(dicyanomethylene)hydrazinyl)benzoic acid (H2L2, 2 ) with methanol (a), ethylenediamine (b), ethanol (c) or water (d) on copper(II), led to a variety of metal complexes, that is, mononuclear [Cu(H2O)2(κO1,κN2 L1a] ( 3 ) and [Cu(H2O)(κO1,κN3 L1b)] ( 4 ), tetranuclear [Cu4(1 κO1,κN2:2 κO1 L2a)3‐(1 κO1, κN2:2 κO2 L2a)] ( 5 ), [Cu2(H2O)(1 κO1, κN2:2 κO1 L2c)‐(1 κO1,1 κN2:2 κO1,2 κN1‐ L2c)]2 ( 6 ) and [Cu2(H2O)2(κO1,κN2‐ L1dd)‐(1 κO1,κN2:2 κO1 L1dd)(μ‐H2O)]2 ? 2 H2O ( 7? 2 H2O), as well as polymer‐ ic [Cu(H2O)(κO1,1 κN2:2 κN1 L1c)]n ( 8 ) and [Cu(NH2C2H5)(κO1,1 κN2:2 κN1L2a)]n ( 9 ). The ligands 2‐SO3H‐C6H4‐(NH)N?C{(CN)[C(NH2)‐(?NCH2CH2NH2)]} (H2L1b, 10 ), 2‐CO2H‐C6H4‐(NH)N?{C(CN)[C(OCH3)‐(?NH)]} (H2L2a, 11 ) and 2‐SO3H‐C6H4‐(NH)N?C{C(?O)‐(NH2)}2 (H2L1dd, 12 ) were easily liberated upon respective treatment of 4 , 5 and 7 with HCl, whereas the formation of cyclic zwitterionic amidine 2‐(SO3?)? C6H4? N?NC(? C?(NH+)CH2CH2NH)(?CNHCH2CH2NH) ( 13 ) was observed when 1 was treated with ethylenediamine. The hydrogen bond‐induced E/Z isomerization of the (HL1d)? ligand occurs upon conversion of [{Na(H2O)2(μ‐H2O)2}(HL1d)]n ( 14 ) to [Cu(H2O)6][HL1d]2 ? 2 H2O ( 15 ) and [{CuNa(H2O)‐(κN1,1 κO2:2 κO1 L1d)2}K0.5(μ‐O)2]n ? H2O ( 16 ). The synthesized complexes 3 – 9 are catalyst precursors for both the selective oxidation of primary and secondary alcohols (to the corresponding carbonyl compounds) and the following diastereoselective nitroaldol (Henry) reaction, with typical yields of 80–99 %. 相似文献
15.
Rajendiran Thekkel M. Kannappan Ramu Mahalakshmy Rajaram Rajeswari Janarthanam Venkatesan Rangarajan Rao Pillutla 《Transition Metal Chemistry》2003,28(4):447-454
A series of binuclear CuII complexes [Cu2XL]
n+ having two copper(II) ions bridged by different motifs (X = OH–, MeCO2
–, or Cl–) have been prepared using the ligands: H2L1 = 4-methyl-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L2 = 4-nitro-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H2L3 = 4-methyl-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol and H2L4 = 4-nitro-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol. The complexes have been characterized by spectroscopic, analytical, magnetic and electrochemical measurements. Cryomagnetic investigations (80–300 K) revealed anti-ferromagnetic exchange between the CuII ions (–2J in the range –50 to –182 cm–1). The strength of anti-ferromagnetic coupling lies in the order: OAc > OH > Cl. Cyclic voltammetry revealed the presence of two redox couples, assigned to CuII/CuII/CuII/CuI/CuI/CuI. The first reduction potential is sensitive to electronic effects from the aromatic ring substituents and steric effect on the donor nitrogens (side arm) of the ligand systems. 相似文献
16.
Paramagnetic copper(II) complexes of the type [Cu(PPh3)(L)] (where L = bifunctional tridentate Schiff bases) were synthesized from the reaction of anthranillic acid with salicylaldehyde (H2L1), 2‐hydroxy‐1‐naphthaldehyde (H2L2), o‐hydroxyacetophenone (H2L3) and o‐vanillin (H2L4) with monomeric metal precursor [CuCl2(PPh3)2]. The obtained complexes were characterized by elemental analysis, magnetic susceptility and spectroscopic methods (FT‐IR, UV–vis and EPR and cyclic voltammetry). EPR and redox potential studies have been carried out to elucidate the electronic structure, nature of metal–ligand bonding and electrochemical features. EPR spectra exhibit a four line pattern with nitrogen super‐hyperfine couplings originating from imine nitrogen atom. These planar complexes possess a significant amount of tetrahedral distortion leading to a pseudo‐square planar geometry, as is evidenced from EPR properties. Cyclic voltammograms of all the complexes display quasireversible oxidations, Cu(III)? Cu(II), in the range 0.31–0.45 V and reduction peaks, Cu(II)? Cu(I),in the range ?0.29 to ?0.36 V, involving a large geometrical change and irreversible. The observed redox potentials vary with respect to the size of the chelate ring of the Schiff base ligands. Further, the catalytic activity of all the complexes has been found to be high towards the oxidation of alcohols into aldehydes and ketones in the presence of N‐methylmorpholine‐N‐oxide as co‐oxidant. The formation of high valent CuIV?O oxo species as a catalytic intermediate is proposed for the catalytic process. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(10):1750-1764
Reactions of copper(I) halides with triphenyl phosphine in acetonitrile followed by the addition of salicylaldehyde N-ethylthiosemicarbazone {(2-OH–C6H4)(H)C2=N3–N2H–C1(=S)N1HEt, H2stsc-NEt} in chloroform in 1?:?2?:?1 (Cl) or 1?:?1?:?1 (Br, I) molar ratios yield mononuclear, [CuCl(η 1-S-H2stsc-NHEt)(PPh3)2] (1) and sulfur-bridged dinuclear, [Cu2X2(μ-S-H2stsc-NEt)2(PPh3)2] (X?=?Br, 4; I, 5) complexes. Similarly, reaction of silver halides (Cl, Br) with H2stsc-NEt in acetonitrile followed by the addition of PPh3 to the solid that formed (1?:?1?:?2 molar ratio), yielding mononuclear complexes, [AgX(η 1-S-H2stsc-NHEt)(PPh3)2] (Cl, 2; Br, 3). All these complexes are characterized with analytical data, IR, and NMR spectroscopy and single-crystal X-ray crystallography. The ligand favored η 1-S bonding in 1, 2, and 3, and μ-S bonding in 4 and 5. Cu?···?Cu contacts were 3.063?Å. The complexes form 1-D or 2-D H-bonded networks, entrapping solvent in some cases. 相似文献
18.
Yang Liu Stefan G. Resch Iris Klawitter George E. Cutsail Serhiy Demeshko Sebastian Dechert Fritz E. Kühn Serena DeBeer Franc Meyer 《Angewandte Chemie (International ed. in English)》2020,59(14):5696-5705
A neutral hybrid macrocycle with two trans‐positioned N‐heterocyclic carbenes (NHCs) and two pyridine donors hosts copper in three oxidation states (+I–+III) in a series of structurally characterized complexes ( 1 – 3 ). Redox interconversion of [LCu]+/2+/3+ is electrochemically (quasi)reversible and occurs at moderate potentials (E1/2=?0.45 V and +0.82 V (vs. Fc/Fc+)). A linear CNHC‐Cu‐CNHC arrangement and hemilability of the two pyridine donors allows the ligand to adapt to the different stereoelectronic and coordination requirements of CuI versus CuII/CuIII. Analytical methods such as NMR, UV/Vis, IR, electron paramagnetic resonance, and Cu Kβ high‐energy‐resolution fluorescence detection X‐ray absorption spectroscopies, as well as DFT calculations, give insight into the geometric and electronic structures of the complexes. The XAS signatures of 1 – 3 are textbook examples for CuI, CuII, and CuIII species. Facile 2‐electron interconversion combined with the exposure of two basic pyridine N sites in the reduced CuI form suggest that [LCu]+/2+/3+ may operate in catalysis via coupled 2 e?/2 H+ transfer. 相似文献
19.
Prof. Dr. Tarlok S. Lobana Poonam Kumari Ray J. Butcher Jerry P. Jasinski James A. Golen 《无机化学与普通化学杂志》2012,638(11):1861-1867
Reactions of copper(II) acetate with N1‐subsitituted salicylaldehyde thiosemicarbazones [R1R2C2=N3–N2H–C1(=S)–N1HR3;R1 = 2‐HO–C6H4–, R2 = H : R3 = Me (H2L1), Et (H2L2)] are described. Copper(II) acetate was reacted with H2L1 and H2L2 ligands in the presence of polypyridyl co‐ligands, and this led to the formation ofmononuclear complexes, [Cu(κ3‐O, N, S‐L1)(κ2‐N, N‐bipy)] ( 1 ),[Cu(κ3‐O, N, S‐L)(κ2‐N, N‐phen)] [L = L1 ( 3 ), L2 ( 4 )], [Cu(κ3‐O, N, S‐L)(κ2‐N, N‐tmphen)] [L =L1 ( 5 ), L2 ( 6 )] and a dinuclear complex, [Cu2L22(bipy)] ( 2 ) (bipy = 2, 2′‐bipyridine, phen = 1, 10‐phenanthroline, tmphen = 3, 4, 7, 8‐tetramethyl‐1, 10‐phenanthroline). In dinuclear complex 2 , one ligand is O, N3,S‐chelating, while second is O, N3,S‐chelation‐cum‐N2‐bridging; and in all others thio‐ligands are O, N3,S‐chelating. The μeff values for the complexes lie in the range of 1.79–1.83 BM. Complexes 1 , 3 – 6 have square pyramidal arrangement, whereas complex 2 has two independent molecules in the crystal lattice, and each molecule has trigonal bipyramidal square planar (5:4) coordination pair. Complexes 2 , 4 , and 6 showed fluorescence properties. 相似文献
20.
Sabine Löw Jonathan Becker Christian Würtele Andreas Miska Dr. Christian Kleeberg Prof. Dr. Ulrich Behrens Dr. Olaf Walter Prof. Dr. Siegfried Schindler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(17):5342-5351
Mixing CuCl2 ? 2 H2O with benzylamine in alcoholic solutions led to an extremely colorful chemistry caused by the formation of a large number of different complexes. Many of these different species could be structurally characterized. These include relatively simple compounds such as [Cu(L1)4Cl2] (L1=benzylamine) and (HL1)2[CuCl4]. Most interestingly is the easy formation of two cluster complexes, one based on two cluster units Cu4OCl6(L1)4 connected through one [Cu(L1)2Cl2] complex and one based on a cubane‐type cluster ([Cu4O4](C11H14)4Cl4). Both clusters proved to be highly reactive in a series of oxidation reactions of organic substrates by using air or peroxides as oxidants. Furthermore, it was possible to isolate and structurally characterize ([Cu(L1)Cl]3 and [Cu(benz2mpa)2]CuCl2 (benz2mpa=benzyl‐(2‐benzylimino‐1‐methyl‐propylidene)‐amine), two copper(I) complexes that formed in solution, demonstrating the high redox activity of the cluster systems. In addition, it was possible to solve the molecular structures of the compounds Cu4OCl6(MeOH)4, [Cu(MeOH)2Cl2], [Cu(aniline)2Cl2], and an organic side product (HC13H19NOCl). In fact all determined structures are of a known type but the chemical relation between these compounds could be explained for the first time. The paper describes these different compounds and their chemical equilibria. Some of these complexes seem to be relevant in catalytic oxidation reactions and their reactivity is discussed in more detail. 相似文献